The invention relates to novel methylene-dioxybenzenes comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring and aliphatic chains comprising at least one quaternized unsaturated ring, to their use as oxidation dye precursors for the oxidation dyeing of keratin fibres, to dye compositions containing them and to oxidation dyeing processes using them.
It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular para-phenylenediamines, ortho-aminophenols or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives, which are generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes by a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain hetero-cyclic compounds such as, for example, indole couplers.
The variety of molecules used as oxidation bases and couplers makes it possible to obtain a wide range of colours.
The so-called xe2x80x9cpermanentxe2x80x9d coloration obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks and it must allow shades of the desired-strength to be obtained and have good resistance to external agents (light, bad weather, washing, permanent-waving, perspiration and friction).
The dyes must also allow white hairs to be covered, and, lastly, they must be as unselective as possible, i.e. they must allow the smallest possible differences in coloration to be produced over the entire length of the same keratin fibre, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
Now, the Applicant has just discovered, entirely surprisingly and unexpectedly, that a novel family of methylenedioxybenzenes of formula (I) defined below, comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring and aliphatic chains comprising at least one quaternized unsaturated ring, are suitable for use as oxidation dye precursor for oxidation dyeing, but also allow dye compositions to be obtained which lead to strong colorations, in a wide range of shades, and which have excellent properties of resistance to the various treatments to which keratin fibres may be subjected. Lastly, these compositions prove to be readily synthesizable.
These discoveries form the basis of the present invention.
A first subject of the invention is thus methylenedioxybenzenes of formula (I) below, and the addition salts thereof with an acid: 
in which:
Ra and Rb, which may be identical or different, can represent a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 hydroxyalkyl radical or can form, together with the carbon atom to which they are attached, a saturated 5-, 6- or 7-membered carbon-based ring;
R1, R2 and R3, which may be identical or different, represent a hydrogen atom; a halogen atom; a group Z as defined below; a group Axe2x80x2 as defined below; a (C1-C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl radical; an Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl radical; an Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyl radical; an N,N-di(C1-C6)alkylamino(C1C6)alkylcarbonyl radical; an amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a carboxyl radical; a (C1-C6)alkylcarboxyl radical; a C1-C6 alkylsulphonyl radical; an aminosulphonyl radical; an Nxe2x80x94Z-aminosulphonyl radical; a C1-C6N-alkylaminosulphonyl radical; an N,N-di(C1-C6)alkylaminosulphonyl radical; a C1-C6aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl (C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a carbamyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl radical; an N,N-di(C1-C6)alkylcarbamyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a cyano radical; a group OR6 or SR6; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals; an amino(C1-C6)alkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two identical or different radicals chosen from alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyl or N,N-di(C1-C6)alkylcarbamyl, C1-C6 alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl and thiocarbamyl radicals, or from the groups Z defined below, or which are able to form, with the nitrogen atom to which they are attached, a 5- or 6-membered carbon-based ring or a ring containing one or more hetero atoms;
R6 denotes a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a group Z; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a carboxy(C1-C6)alkyl radical; a (C1-C6)alkylcarboxy-(C1-C6)alkyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl (C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl (C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two identical or different radicals chosen from C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, formyl, trifluoro-(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyl, N,N-di-(C1-C6)alkylcarbamyl, thiocarbamyl and C1-C6 alkylsulphonyl radicals, and from the groups Z; or which are able to form, together with the nitrogen atom to which they are attached, a 5- or 6-membered carbon-based ring or a ring containing one or more hetero atoms;
A represents a group xe2x80x94NR4R5 or a hydroxyl radical;
Axe2x80x2 represents a group xe2x80x94NRxe2x80x24Rxe2x80x25 or a hydroxyl radical;
R4, R5, Rxe2x80x24 and Rxe2x80x25, which may be identical or different, represent a hydrogen atom; a group Z; a C1-C6alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical; a benzyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; a thiocarbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 sulphoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 Nxe2x80x94Z-aminosulphonylalkyl radical; an Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylcarbonyl(C1-C6)alkyl radical; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals; a C1-C6 aminoalkyl radical in which the alkyl is unsubstituted or substituted with one or more hydroxyl radicals and in which the amine is substituted with one or two identical or different radicals chosen from C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)alkylcarbonyl, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl and thiocarbamyl radicals, or from the groups Z, or which are able to form, together with the nitrogen atom to which they are attached, a 5- or 6-membered carbon-based ring or a ring containing one or more hetero atoms;
Z is chosen from the unsaturated cationic groups of formulae (II) and (III) below, and the saturated cationic groups of formula (IV) below: 
xe2x80x83in which:
D is a linker arm which represents a linear or branched alkyl chain preferably containing from 1 to 14 carbon atoms, which can be interrupted by one or more hetero atoms such as oxygen, sulphur or nitrogen atoms, and which can be substituted with one or more hydroxyl or C1-C6 alkoxy radicals, and which can bear one or more ketone functions;
the ring members E, G, J, L and M, which may be identical or different, represent a carbon, oxygen, sulphur or nitrogen atom;
n is an integer between 0 and 4 inclusive;
m is an integer between 0 and 5 inclusive;
the radicals R, which may be identical or different, represent a second group Z which is identical to or different from the first group Z, a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a cyano(C1-C6)alkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a (C1-C6)alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a C1-C6 alkylthio radical, an amino radical, an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3 Rxe2x80x2xe2x80x3 in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which may be identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
R7 represents a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a cyano(C1-C6)alkyl radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a carbamyl(C1-C6)alkyl radical, a (C1-C6)alkylcarboxy(C1-C6)alkyl radical, a benzyl radical or a second group Z which is identical to or different from the first group Z;
R8, R9 and R10, which may be identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a cyano(C1-C6)alkyl radical, an aryl radical, a benzyl radical, a C1-C6 amidoalkyl radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical or a C1-C6 aminoalkyl radical in which the amine is protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; two of the radicals R8, R9 and R10 can together also form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered carbon-based ring or a ring containing one or more hetero atoms such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be unsubstituted or substituted with a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a cyano(C1-C6)alkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6)alkylsilane(C1-C6)alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a keto(C1-C6)alkyl radical, a thio radical, a C1-C6 thioalkyl radical, a C1-C6 alkylthio radical, an amino radical or an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical;
one of the radicals R8, R9 and R10 can also represent a second group Z which is identical to or different from the first group Z;
R11 represents a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical, a C1-C6 aminoalkyl radical in which the amine is protected with a (C1-C6)alkylcarbonyl, carbamyl or C1-C6 alkylsulphonyl radical; a carboxy(C1-C6)alkyl radical; a cyano(C1-C6)alkyl radical; a carbamyl(C1-C6)alkyl radical; a C1-C6 trifluoroalkyl radical; a tri(C1-C6)alkylsilane(C1-C6)alkyl radical; a C1-C6 sulphonamidoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyl radical; a (C1-C6)alkylsulphinyl(C1-C6)alkyl radical; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; a (C1-C6)alkylketo(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyl radical; an Nxe2x80x94(C1-C6)alkylsulphonamido(C1-C6)alkyl radical;
a and y are integers equal to 0 or 1; with the following conditions:
in the unsaturated cationic groups of formula (II):
when a=0, the linker arm D is attached to the nitrogen atom,
when a=1, the linker arm D is attached to one of the ring members E, G, J or L,
y can take the value 1 only:
1) when the ring members E, G, J and L simultaneously represent a carbon atom and when the radical R7 is borne by the nitrogen atom of the unsaturated ring; or alternatively
2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R7 is attached;
in the unsaturated cationic groups of formula (III):
when a=0, the linker arm D is attached to the nitrogen atom,
when a=1, the linker arm D is attached to one of the ring members E, G, J, L or M,
y can take the value 1 only when at least one of the ring members E, G, J, L and M represents a divalent atom and when the radical R7 is borne by the nitrogen atom of the unsaturated ring;
in the cationic groups of formula (IV):
when a=0, then the linker arm D is attached to the nitrogen atom bearing the radicals R8 to R10,
when a=1, then two of the radicals R8 to R10 form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above, and the linker arm D is borne by a carbon atom of the said saturated ring;
Xxe2x88x92 represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a C1-C6 alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate;
it being understood that:
the number of cationic groups Z is at least equal to 1.
As mentioned above, the colorations obtained with the oxidation dye composition in accordance with the invention are strong and produce a wide range of shades and colours. They moreover have excellent properties of resistance to the action of various external agents (light, bad weather, washing, permanent-waving, perspiration, friction). These properties are particularly noteworthy, in particular as regards the resistance of the colorations obtained to the action of light, washing and perspiration.
In formulae (I), (II), (III) and (IV) above, the alkyl and alkoxy radicals can be linear or branched.
Among the carbon-based rings which may be formed, together with the radicals Ra and Rb, mention may be made particularly of pentane, hexane and heptane rings.
Among the rings of the unsaturated groups Z of formula (II) above, mention may be made in particular, for example, of pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
Among the rings of the unsaturated groups Z of formula (III) above, mention may be made in particular, for example, of pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
The compounds of formula (I) above are preferably chosen from:
1-[2-(benzo[1,3]dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
1- [2-(6-hydroxybenzo[1,3]dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[2-(6-methoxybenzo[1,3]dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol1-ium chloride;
1-[2-(6-ethoxybenzo[1,3]dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
1-{2-[6-(2-hydroxyethoxy)benzo[1,3]dioxol-5-yl-amino]ethyl}-3-methyl-3H-imidazol-1-ium chloride;
1-[2-(6-aminobenzo[1,3]dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
1-{2-[6-(2-(3-methyl-3H-imidazol-1-ium)ethoxy)-benzo[1,3]dioxol-5-ylamino]ethyl}-3-methyl-3H-imidazol-1-ium dichloride;
1-[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
1-[3-(6-aminobenzo[1,3]dioxol-5-yloxy)propyl]-3-methyl-3H-imidazol-1-ium chloride;
[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]diethyl-(2-hydroxyethyl)ammonium bromide;
[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]diethyl-methylammonium methyl sulphate;
1-[2-(6-aminobenzo[1,3]dioxol-5-yloxy)ethyl]-1,4-dimethylpiperazin-1-ium chloride;
1-[2-(2,2-bis(hydroxymethyl)-6-methoxybenzo[1,3]-dioxol-5-ylamino)ethyl]-3-methyl-3H-imidazol-1-ium chloride;
and the addition salts thereof with an acid.
The addition salts with an acid of the compounds of formula (I) in accordance with the invention are preferably chosen from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The compounds of formula (I) in accordance with the invention can readily be obtained according to methods that are well known in the prior art, for example by reduction of the corresponding cationic nitro compounds when these compounds bear an amino group.
This reduction step (production of a primary aromatic amine), which may or may not be followed by a salification, is generally, for convenience, the final step of the synthesis.
This reduction can take place earlier in the sequence of reactions leading to the preparation of the compounds of formula (I), and according to well-known processes it is then necessary to xe2x80x9cprotectxe2x80x9d the primary amine created (for example by an acetylation, formylation, benzenesulphonation, etc. step), then carry out the desired substitution(s) or modification(s) (including quaternization) and end by xe2x80x9cdeprotectingxe2x80x9d (generally in acidic medium) the amine function.
Similarly, the phenolic function can be protected according to well-known processes with a benzyl radical (xe2x80x9cdeprotectionxe2x80x9d by catalytic reduction) or with an acetyl or mesyl radical (xe2x80x9cdeprotectionxe2x80x9d in acidic medium).
The cationic chains are themselves obtained by methods that are well known in the prior art.
The production of the quaternized amines can be carried out, for example:
in one step, by condensation of a methylenedioxybenzene compound comprising a haloalkyl radical with a compound bearing a tertiary amine radical, or by condensation of a methylenedioxybenzene compound comprising a tertiary amine radical with a compound bearing a haloalkyl radical, or by quaternization of a methylenedioxybenzene compound comprising a tertiary amine radical with an alkylating agent;
or in two steps, by condensation of a methylenedioxybenzene compound comprising a haloalkyl radical with a compound bearing a secondary amine, followed by quaternization with an alkylating agent.
The haloalkyl radicals borne by the intermediate methylenedioxybenzene compounds can be prepared by methods that are well known in the prior art, in one or more steps, for/example by condensation of a dihaloalkyl compound with an amine or a hydroxyl, or by halogenation of a hydroxyalkyl chain.
When the synthesis is complete, the compounds of formula (I) in accordance with the invention can, if necessary, be recovered by methods which are well known in the state of the art, such as crystallization or distillation.
Another subject of the invention is the use of the compounds of formula (I) in accordance with the invention as oxidation dye precursor for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
The invention also relates to a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it comprises as oxidation dye, in a medium which is suitable for dyeing, at least one compound of formula (I) in accordance with the invention.
The compound(s) of formula (I) in accordance with the invention preferably represent(s) from 0.0005% to 12% by weight approximately relative to the total weight of. the dye composition, and even more preferably from 0.005% to 6% by weight approximately relative to this weight.
The medium which is suitable for dyeing (or the support) generally consists of water or a mixture of water and at least one organic solvent. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.
The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres.
Among the acidifying agents which may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the basifying agents which may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such/as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (V) below: 
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R12, R13, R14 and R15, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.
In addition to the compound(s) of formula (I) defined above, the dye composition in accordance with the invention can also contain at least one oxidation base which may be chosen from the oxidation bases conventionally used for oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines which can be mentioned more particularly, for example, are para-phenylenediamine, para-tolylenediamine, 2-chloro-para-penylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylene-diamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2, xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine and N-(xcex2-methoxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.
Among the bis(phenyl)alkylenediamines which can be mentioned more particularly, for example, are N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)-tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)-ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.
Among the para-aminophenols which can be mentioned more particularly, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
Among the ortho-aminophenols which can be mentioned more particularly, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
Among the heterocyclic bases which can be mentioned more particularly, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives which may be mentioned more particularly are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the addition salts thereof with an acid.
Among the pyrimidine/derivatives which may be mentioned more particularly are the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 96-10659 or patent application Wo 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminoprazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxy-ethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino)ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 3-amino-5-methyl-7-imidazolylpropyl-aminopyrazolo[1,5-a]pyrimidine, the tautomeric forms thereof, when a tautomeric equilibrium exists, and the addition salts thereof with an acid.
Among the pyrazole derivatives which may be mentioned more particularly are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethyl-pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropyl-pyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethyl-pyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylamino-pyrazole and 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof with an acid.
When they are used, these oxidation bases preferably represent from 0.0005% to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005% to 6% by weight approximately relative to this weight.
The oxidation dye compositions in accordance with the invention can also contain one or more couplers and/or one or more direct dyes, in particular to modify the shades or to enrich them with glints.
The couplers which can be used in the oxidation dye compositions in accordance with the invention can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylene-diamines, meta-aminophenols and meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and the addition salts thereof with an acid.
These couplers are chosen more particularly from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof with an acid.
When they are present, these couplers preferably represent from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
In general, the addition salts with an acid which can be used in the context of the invention (compounds of formula (I), oxidation bases and couplers) are chosen in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents such as, for example, silicones, film-forming agents, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
The dye composition according to the invention can be in various forms, such as in the form of liquids, creams or gels or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.
The invention also relates to a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.
A subject of the invention is also a process for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, using the dye composition as defined above.
According to this process, at least one dye composition as defined above is applied to the fibres, for a period which is sufficient to develop the desired coloration, either in air or using an oxidizing agent. The dye composition can optionally contain oxidation catalysts, in order to accelerate the oxidation process.
According to a first embodiment of the process of the invention, the coloration of the fibres can be carried out without adding an oxidizing agent, merely by contact with atmospheric oxidation.
According to a second embodiment of the process of the invention, and in particular when the dye composition in accordance with the invention contains one or more oxidation bases and/or one or more couplers, at least one dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added to the dye composition just at the time of use, or which is present in an oxidizing composition which is applied simultaneously or sequentially in a separate manner.
According to this second embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium which is suitable for dyeing, at least one oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and is left in place for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates and persalts such as perborates and persulphates, and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases, among which mention may be made in particular of pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.
The pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resultant composition applied to the keratin fibres preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It is adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres and as defined above.
The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The composition which is finally applied to the keratin fibres can be in various forms, such as in the form of liquids, creams, gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.
Another subject of the invention is a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices can be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2,586,913 in the name of the Applicant.